Recrystallization of Acetanilide Reyes, K.B., Rivera, G.I., Samonte, A.A., Soliven, R.Y.*, Sotto, K.C.

2CMT, Faculty of Pharmacy, UST
Abstract Recrystallization is the primary method for purifying solid organic compounds through the differences in solubility at different temperatures. The dissolved solid has a decreased solubility at lower temperature and separates from the solution as it is cooled. A small seed crystal is formed initially, and it then grows layer by layer. In this experiment, acetanilide was formed by the acetylation of aniline and acetic anhydride. The crude acetanilide was dissolved in a solvent in a hot water bath. The solution was then cooled in an ice bath as crystals start to form. As the compound formed crystals, molecules of other compounds dissolved in the solution are excluded from the growing layer of crystals; hence, pure acetanilide is formed.

Introduction Organic compounds that are synthesized in laboratories or isolated from natural recourses are often tainted by impurities. Recrystallization is a process that removes these impurities from solid organic compounds that are at room temperature. This process is built on the principle that the solubility of a compound increases with temperature and decreases as it cools down, into its crystal form. Very pure compounds can be made by recrystallization. A small pure seed crystal of the compound forms in the solution as it cools down after being heated. Additional molecules are attached to the crystal in uniform layers, forming a growing crystal lattice. Crystal molecules have a higher affinity for the same kind of molecules than impurities. This process of crystallizing removes one kind of molecule from the solution. Recrystallization is a method in which two crystallization processes were performed. It is usually known as the second crystallization. It depends on the difference of solubility of a substance in a hot and in a cold solvent. Solubility refers to the degree of substance which is the solute to be dissolved in solvent. It is the main factor that affects crystallization. Prior to the recrystallization process, identifying the recrystallizing solvent is necessary. The substance to be crystallized must exhibit ideal solubility behavior in the chosen solvent. Purification of substances can take place when both the substance to be purified and the impurities have similar solubility at its boiling point temperature; and the impurities correspond to only a small portion of the total solid. In this manner, the substance to be purified would be the only one crystallized.

Figure 1 Structure of Aniline Aniline   is a primary amine in which the amino group is directly attached to the benzene ring and the final product of the reduction of most nitrogen derivatives of benzene. It has a density of 1.0217 g/ml and a molecular weight of 93.13 g/mol. Aniline is a clear to slightly yellow liquid with a characteristic odor. It does not readily evaporate at room temperature. Aniline is slightly soluble in water and mixes readily with most organic solvents. It is used to make a wide variety of products such as polyurethane foam, agricultural chemicals, synthetic dyes, antioxidants, stabilizers for the rubber industry, herbicides, varnishes and explosives. When exposed to light and air, it slowly changes color. It darkens because

The test tube was shaken and placed in a warm water bath (3740°C) for 1-5 minutes. It was then placed in a hot water bath until the solid dissolved. penetrating. glycerol.09 g/mol.082 g/ml and a molecular weight of 102. however.of atmospheric oxidation of an impurity usually present in the benzene from which the aniline was prepared. Phenylacetamide structure shows analgesic and antipyretic effects. It is used as a precursor in penicillin synthesis and other pharmaceuticals including painkillers and intermediates. and calculate the percentage yield of the pure acetanilide. Then. ether. The experiment aims to synthesize acetanilide by the acetylation of aniline. it was cooled through an ice water bath. It has a density of 1. but is otherwise stable under most conditions. Acetanilide is used as an inhibitor of peroxides and stabilizer for cellulose ester varnishes. It is also used in the manufacture of pigments. It is an odorless. Acetic anhydride is used in the manufacture of cellulose acetate having the application as a base for magnetic tape and in the manufacture of textile fibres. which is more commonly known as acetanilide. To produce crude acetanilide. Aniline is acetylated by warming a mixture of aniline and acetic anhydride. methanol and hexane were used respectively using the same procedure. the solution was placed in an ice bath then filtered through a wet filter paper. cellulose and pesticides etc. and benzene. Also. chloroform and benzene. chloroform. purify crude acetanilide product by recrystallization. white flake solid or crystalline powder (pure form). 1-ml of water was added to the first test tube. It can . Acetanilide is soluble in hot water. It melts at a range of 114-116°C and boils at 304°C. alcohol. Figure 2 Structural formula of Acetic anhydride Acetic Anhydride or Acetyl Ether is a clear. For the second and third test tubes. it plays an important role in the acetylation of aniline to form acetanilide. acetanilide is not used directly for it may cause methemoglobinemia (the presence of excessive methemoglobin which does not function reversibly as an oxygen carrier in the blood). A 3-ml acetic anhydride was then added slowly into the solution. dyes. Most importantly. A 20-ml recyrstallizing solvent was poured into the crude acetanilide. vinegar-like odor that combines with water to form acetic acid. It is used as an intermediate for the synthesis of rubber accelerators. dyes and dye intermediate and camphor. Methodology A corn-grain amount of acetanilide was placed into each of the three test tubes. To hasten crystallization. forming Nphenylacetamide. undergo self-ignite at 545 C. 2-ml of aniline and 20-ml distilled water were mixed in an Erlenmeyer flask. acetone. The crude acetanilide was dried and weighed by the use of an analytical balance. colorless liquid with a very pungent. Its boiling point is at 140°C while its melting point is at -73°C. it is heated with salicylic acid to produce acetylsalicylic acid (aspirin). Observations were recorded. It is soluble in ether. Figure 3 Structural formula of Acetanillide Acetanilide [C6H5NH(COCH3)] or NPhenylacetamide is the product of acetylation of aniline with acetic anhydride at low temperature. All changes that took place were noted.

any undissolved impurities can be removed by filtration. At room temperature it was insoluble. This way. It was then placed inside the locker until next meeting. Second. In contrast. distilled water exhibited a different result. the temperature is lowered so that heat shall be removed. Third. After the solution cools and the desired compound Methanol Hexane Table 1 Solubility of Pure Acetanilide in Different Solvent Three solvents (distilled water. any remaining soluble impurities will remain dissolved in the solvent. This allows for easy and rapid drying of the solid compound after it has been isolated from the solution. and upon cooling. There are four important properties that you should look for in a good solvent for recrystallization. when placed on these two solvents. Thus. Thus. the unwanted impurities should be either very soluble in the solvent at room temperature or insoluble in the hot solvent. The desired compound may be lost during recrystallization if the solvent reacts with the compound. it was insoluble. Therefore. the solvent should not react with the compound being purified. Lastly. . The crystals were collected. A compound usually exhibits one of three general solubility behaviors: (1). Identifying the ideal recrystallizing solvent of a compound is necessary to purify the organic compound.If the solution is colored. Results and Discussion crystallizes out. it must be removed from the water bath and a small amount of activated charcoal must be added to adsorb the colored impurities. that is. Both methanol and hexane are flammable and volatile. and (3). high solubility at high temperatures and low solubility at low temperatures. the compound has a low solubility in both hot and cold solvent. acetanilide. cannot undergo recrystallization. The filtrate was allowed to cool by placing the receiver in a beaker containing tap water. During cooling. after the impure solid is dissolved in the hot solvent. extra caution must be utilized. during heating it was soluble. Recrystallizing solvent is a solvent that shows the desired solubility behavior for the substance to be crystallized. determined. Insoluble Soluble Insoluble During heating Soluble Soluble Insoluble Upon cooling Insoluble Soluble Insoluble Water The primary step involved in recrystallization is selecting a suitable solvent. crystals form. Hence. the compound has a high solubility in both hot and cold solvent. The solvent should be volatile enough to be easily removed from the solvent after the compound has crystallized. Solvent Room temp. producing acetanilide exhibits release of heat or exothermic reaction. The pure acetanilide collected was weighed using an analytical balance. However. methanol. and hexane) were tested. Absorption of heat is exhibited when acetanilide is placed in a hot water bath. methanol is soluble and hexane is insoluble at room temperature. Solvents which exhibit the first two behaviors are not useful for recrystallizing a compound. the reaction of aniline with acetic anhydride. However. if the solution is colorless. (2). Water shows the desired solubility behavior of an ideal recrystallizing solvent. and upon cooling. the solute dissolves in the solvent. The first characteristic of a good recrystallizing solvent is exhibited by a solvent showing the third behavior. As shown in Table 1. it must be quickly filtered while still hot using a fluted filter paper. washed with distilled water and dried by pressing-in between filter paper. during heating. The melting point was likewise. the compound has a high solubility in hot solvent and a low solubility in cold solvent.

hence. the solution was placed in a hot water bath. the solution would look as if it was colored because of impurities.          Identify the limiting reagent:     Hence. On the other hand. Take note that premature recrystallization may occur when the solution in the flask was not kept in its boiling point temperature. the solution should be immediately filtered in an ice water bath while still hot. The weight of the pure acetanilide collected was reduced to 1.Hastening of crystallization is done through ice water bath which decreases the solubility of acetanilide. during filtration. To reduce the amount of mother liquor. Filtration is the most effective way to remove unwanted impurities most especially when decolorization was utilized. the crystals were dried by pressing-in between filter paper. However. This is the pure . washing of crystals with cold distilled water must be done. just a small amount of activated charcoal should be added. After filtration. It would be noted that the recrystallizing solvent is not enough to dissolve the substance which may result to reduction of the crystallized acetanilide. limiting reagent is the reactant that is used up first in a reaction. the Aniline (  ).00 g 64% Table 2 The actual yield of crude and pure acetanilide. Weight of the crude acetanilide Weight of acetanilide Percentage Yield pure 2. However.00 g. These impurities may be decolorized by the use of activated charcoal which adsorbs impurities because it has a large surface area and it can remove impurities more effectively. Evaporation of solvent may initiate premature crystallization.24 g.24 g 1. During recrystallization. During the water bath in recrystallization. The theoretical yield is the maximum yield of pure crystals that could be obtained by cooling or evaporating a given solution. This refers to the quantity of pure crystals deposited from the solution. The acetylation of aniline and acetic anhydride would yield to acetanilide but it may contain small amount of impurities which may affect the weight of pure acetanilide. some were not weighed because the crystals were attached to some part of the filter paper. limiting  reagent  is Theoretical yield = mass of LR       The percentage yield based on the experiment is 49%. and the percentage yield of pure acetanilide The weight of the crude acetanilide is 2. some part of the solution was lost that resulted to reduction of the pure acetanilide. To calculate the percentage yield. Too much activated charcoal will also adsorb the desired substance. Mother liquor refers to the solution that remains in the crystals. the theoretical yield and the limiting reagent must be first identified. However.

D. (1999). 2010. Pg. The melting point of pure acetanilide was also determined by immersing a capillary tube with pure acetanilide attached to a thermometer into an oil bath. M. Cruz. the recrystallized acetanilide obtained is pure. A. from http://chemicalland21.pdf RECRYSTALLIZATION SOLVENT.acetanilide obtained from the 2-ml aniline and 3-ml acetic anhydride.com/petrochemical /ACETIC%20ANHYDRIDE.chem.edu/JCESoft/C CA/CCA6/MAIN/1ChemLabMenu/Separatin g/F_1SOLVE_MENU/F_1SOLVE/F_1SOLVE _01/F_1SOLVE_10/MOVIE. 558576 Web sites: ACETANILIDE (N-PHENYLACETAMIDE). 2010. C. 2010.).edu/~samal/269 /cryst1. (n. G.. G. The melting point of the crude acetanilide ranges from 115-118°C while the pure acetanilide melts at 110-116°C. Retrieved August 21. Pg. Retrieved August 21..d. Hence. Retrieved August 22.wisc.htm ACETIC ANHYDRIDE (ACETYL ETHER).htm PURIFYING ACETANILIDE BY RECRYSTALLIZATION.umass.cerlabs. Lampman. References Books: Bayquen. G. 4748 Pavia. R. Organic Laboratory Techniques: A Microscale Approarch (3rd Ed.com/lifescience/pha r/ACETANILIDE. Philippines: C & E Publishing. Inc.chem. Laboratory Manual in Organic Chemistry. from http://chemicalland21.com/experiments/108 7540703X.).pdf .. from http://jchemed. from http://www. (n. et. from http://www. (2009). 2010. Retrieved August 21. & Engel.HTM RECRYSTALLIZATION Retrieved August 21. Harcourt College Publiser. S..al. L.d. Kriz. 2010.).

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